F. Touchard, F. Fache, M. Lemaire
55.5 (CH), 126Ϫ141.9 (Caro), 135.9 (NCS). Ϫ C22H13N3S3 (415.5) 233Ϫ235; [α]2D0 ϭ Ϫ182 (c ϭ 0.5, DMSO). Ϫ IR: ν˜ ϭ 3391, 3063,
FULL PAPER
calcd. C 63.59, H 3.15, N 10.11, S 23.15; found C 63.77, H 3.02,
N 10.08, S 23.13.
2947, 2080, 1600, 1495, 1326, 1077, 766, 701. Ϫ 1H NMR
([D6]DMSO): δ ϭ 2.67 (br. s, CH3), 3.37 (br. s, NMe), 7.41 (br. s,
CH), 7.71 (br. s, CH), 8.23 (br. s, CH), 9.66 (s, NH). Ϫ 13C NMR:
δ ϭ 18.4 (CH3), 33.8 (NMe), 60.3 (CH), 125.7Ϫ137.8 (Caro), 182.4
(NCS). Ϫ C384H340N38S20 (6128) calcd. C 75.52, H 5.71, N 8.67, S
10.10; found C 75.26, H 5.59, N 8.69, S 10.46.
Polymer Synthesis: Diisothiocyanate (2.06 mmol) was dissolved in
the minimum possible volume of CH2Cl2. Diamine (2.09 mmol) in
CH2Cl2 (1 mL) was then added. The reaction mixture was stirred
for 12 h under Ar. iPrOH (50 mL) was added and the reaction mix-
ture was allowed to stir for 12 h. The polymer precipitated and was
recovered by filtration. After washing with iPrOH, it was dried un-
der vacuum for two days.
Polymer 18: This polymer was obtained according to the procedure
described above, starting from diisocyanate 8. Yield: 56%; mp:
215Ϫ217 °C; [α]D20 ϭ 200 (c ϭ 0.5, DMSO). Ϫ IR: ν˜ ϭ 3388, 3029,
2917, 2086, 1602, 1499, 1332, 1227, 1077, 862, 700. Ϫ 1H NMR
([D6]DMSO): δ ϭ 2.23 (s, CH3), 2.35 (s, CH3), 2.42 (s, CH3), 3.13 (s,
NMe), 7.23Ϫ7.6 (m, CH), 8.07 (br. s, CH), 9.01 (br. s, NH). Ϫ 13C
NMR: δ ϭ 18.1Ϫ18.4 (3CH3), 33.4 (NMe), 60.2 (CH), 125.7Ϫ138
(Caro), 181.4 (NCS). Ϫ C460H484N54S28 (7667) calcd. C 72.11, H 6.33,
N 9.76, S 11.80; found C 72.06, H 6.36, N 9.87, S 11.71.
Polymer 12: This polymer was obtained according to the procedure
described above, starting from diisocyanate 2. Yield 45%; mp:
202Ϫ204 °C; [α]2D0 ϭ Ϫ470 (c ϭ 0.5, DMSO). Ϫ IR: ν˜ ϭ 3346, 3051,
2936, 1531, 1455, 1391, 1341, 1233, 1186, 1071, 788, 705. Ϫ 1H
NMR ([D6]DMSO): δ ϭ 1.56 (s, CH2), 2.81 (s, NMe), 3.59 (s, CH2),
7.25 (d, J ϭ 8 Hz, CHaro), 7.52 (d, J ϭ 7 Hz, CHaro), 7.83 (CHaro).
Ϫ
13C NMR: δ ϭ 26.2 (CH2), 32.6 (CH2), 45.5 (CH2), 59.9 (CH),
Polymer 19: This polymer was obtained according to the procedure
described above, starting from diisocyanate 9. Yield: 81%; mp:
213Ϫ215 °C; insoluble in every tested solvent. Ϫ IR: ν˜ ϭ 3387,
3235, 3057, 2938, 2037, 1619, 1596, 1499, 1320, 1075, 817, 754, 700.
127.6Ϫ137.9 (Caro), 181.5 (CS). Ϫ (C22H28N4S2)n calcd. C 64.08, H
6.79, N 13.59, S 15.53; found C 63.84, H 6.77, N 13.74, S 15.65.
Polymer 13: This polymer was obtained according to the procedure
described above, starting from diisocyanate 3. Yield: 81%; mp:
207Ϫ209 °C; [α]2D0 ϭ Ϫ355 (c ϭ 0.51, DMSO); IR: ν˜ ϭ 3346, 3050,
2944, 2030, 1628, 1596, 1527, 1319, 1153, 1110, 1075, 837, 702. Ϫ
1H NMR ([D6]DMSO): δ ϭ 2.47 (s, NMe), 3.11 (s, NMe), 7.27 (m,
CH), 7.59 (m, CH), 7.86 (br. s, CH), 9.51 (NH). Ϫ 13C NMR: δ ϭ
33.4 (NMe), 34.1 (NMe), 60.2 (CH), 71.7 (CH), 125.7Ϫ145.6
(Caro), 181.9 (NCS). Ϫ C450H418N60O30S44 (8546) calcd. C 63.19,
H 4.89, N 9.83, S 16.48; found C 62.92, H 4.89, N 9.50, S 16.88.
1
Ϫ H NMR ([D6]DMSO. Ϫ 100 °C): δ ϭ 2Ϫ2.5 (m, NMe), 3.00
(m, NMe), 6.66Ϫ8 (m, CH). Ϫ 13C NMR: δ ϭ 33.9 (NMe), 61.1
(CH), 122.7Ϫ138.5 (Caro), 182.6 (NCS). Ϫ C532H446N56S27 (8489)
calcd. C 75.48, H 5.11, N 9.07, S 10.33; found C 75.27, H 5.29, N
9.24, S 10.20.
Polymer 20: This polymer was obtained according to the procedure
described above, starting from diisocyanate 10. Yield: 87%; mp:
208Ϫ210 °C; [α]2D0 ϭ Ϫ412 (c ϭ 0.5, DMSO). Ϫ IR: ν˜ ϭ 3391, 3058,
2932, 1618, 1593, 1500, 1320, 1081, 817, 754, 700. Ϫ 1H NMR
([D6]DMSO): δ ϭ 2Ϫ2.8 (m, NMe), 6.3Ϫ8.4 (m, CH). Ϫ 13C NMR:
δ ϭ 33.1Ϫ37.1 (NMe), 60.4Ϫ60.9 (CH), 73.1 (CH), 126.8Ϫ138.4
(Caro), 183.1 (NCS). Ϫ C342H286N36S17 (5445) calcd. C 75.58, H
5.19, N 9.18, S 10.05; found C 75.44, H 5.29, N 9.26, S 10.01.
Polymer 14: This polymer was obtained according to the procedure
described above, starting from diisocyanate 4. Yield: 87%; mp:
207Ϫ209 °C; [α]2D0 ϭ Ϫ339 (c ϭ 0.51, DMSO). Ϫ IR: ν˜ ϭ 3367,
3027, 2921, 2080, 1599, 1515, 1332, 1230, 1073, 760, 700. Ϫ 1H
NMR ([D6]DMSO): δ ϭ 3.09 (s, NMe), 3.95 (s, CH2), 7.27 (m,
CH), 7.57 (m, CH), 7.96 (s, CH), 9.19 (s, 1 H, NH). Ϫ 13C NMR:
δ ϭ 33.5 (NMe), 40.0 (CH2), 60.2 (CH), 72.1 (CH), 123.7Ϫ138.8
Polymer 21: This polymer was obtained according to the procedure
(Caro), 182 (NCS). Ϫ C279H268N36S17 (4670) calcd. C 71.82, H 5.78, described above, starting from diisocyanate 11. Yield: 85%. Ϫ IR:
ν
˜ ϭ 3367, 3029, 2927, 2048, 1631, 1598, 1510, 1319, 1227, 1066,
N 10.81, S 11.59; found C 71.75, H 5.78, N 10.80, S 11.67.
698; solid state 13C NMR: δ ϭ 34.9 (NMe), 55.3 (CH), 61.9 (CH),
72.5 (CH), 129.1Ϫ138.5 (Caro), 183.7 (NCS); elemental analysis:
found C 72.68, H 5.73, N 10.73, S 10.86.
Polymer 15: This polymer was obtained according to the procedure
described above, starting from diisocyanate 5. Yield: 72%; mp:
202Ϫ204 °C; [α]2D0 ϭ Ϫ367 (c ϭ 0.51, DMSO). Ϫ IR: ν˜ ϭ 3369,
3029, 2934, 1598, 1520, 1480, 1328, 1223, 1075, 757, 700. Ϫ 1H
NMR ([D6]DMSO): δ ϭ 2.57 (s, NMe), 3.13 (s, NMe), 7.28 (m,
CH), 7.58 (m, CH), 7.98 (m, CH), 9.31 (s, NH). Ϫ 13C NMR: δ ϭ
33.7 (NMe), 60.4 (CH), 72.1 (CH), 124.1Ϫ141.4 (Caro), 182.1
(NCS). Ϫ C232H232N38S16 (4066) calcd. C 68.56, H 5.59, N 13.31,
S 12.54; found C 68.54, H 5.75, N 13.09, S 12.62.
[1]
S. Hashiguchi, A. Fujii, J. Takehara, T. Ikariya, R. Noyori, J.
Am. Chem. Soc. 1995, 117, 7562Ϫ7563; R. Noyori, S. Hashigu-
chi, Acc. Chem. Res. 1997, 30, 97Ϫ102.
L. Schwink, T. Ireland, K. Püntener, P. Knochel, Tetrahedron:
Asymmetry 1998, 9, 1143Ϫ1163.
Y. Jiang, Q. Jiang, X. Zhang, J. Am. Chem. Soc. 1998, 120,
3817Ϫ3818.
F. Touchard, P. Gamez, F. Fache, M. Lemaire, Tetrahedron
Lett. 1997, 38(13), 2275Ϫ2278.
R. ter Halle, E. Schulz, M. Lemaire, Synlett 1997, 1257Ϫ1258.
D. J. Bayston, C. B. Travers, M. E. C. Polywka, Tetrahedron:
Asymmetry 1998, 9, 2015Ϫ2018.
E. Breysse, C. Pinel, M. Lemaire, Tetrahedron: Asymmetry
1998, 9, 897Ϫ900.
P. Gamez, B. Dunjic, F. Fache, M. Lemaire, J. Chem. Soc.,
Chem. Commun. 1994, 1417Ϫ1418.
[2]
[3]
Polymer 16: This polymer was obtained according to the procedure
described above, starting from diisocyanate 6. Yield: 80%; mp:
219Ϫ221 °C; [α]2D0 ϭ Ϫ367 (c ϭ 0.51, DMSO). Ϫ IR: ν˜ ϭ 3369,
3037, 2951, 1631, 1603, 1519, 1478, 1332, 1227, 1075, 700. Ϫ 1H
NMR ([D6]DMSO): δ ϭ 2.63 (s, NMe), 3.13 (s, NMe), 7.34 (m,
CH), 7.59 (m, CH), 7.98 (br. s, CH), 9.29 (br. s, NH). Ϫ 13C NMR:
δ ϭ 33.7 (NMe), 60.3 (CH), 72.3 (CH), 126.4Ϫ140 (Caro), 182.1
(NCS). Ϫ C328H328N54S22 (5800) calcd. C 68.00, H 5.76, N 12.96,
S 13.28; found C 67.97, H 5.70, N 13.05, S 13.28.
[4]
[5]
[6]
[7]
[8]
[9]
S. Kim, K. Y. Yi, J. Org. Chem. 1986, 51, 2613Ϫ2615.
Polymer 17: This polymer was obtained according to the procedure
described above, starting from diisocyanate 7. Yield: 87%; mp:
Received February 3, 2000
[O00069]
3792
Eur. J. Org. Chem. 2000, 3787Ϫ3792